Mineralium Deposita

, Volume 42, Issue 7, pp 691–713 | Cite as

Stable isotope study of the mineralization and alteration in the Madjarovo Pb–Zn district, south-east Bulgaria

  • Clive M. Rice
  • Richard J. McCoyd
  • Adrian J. Boyce
  • Peter Marchev


The Madjarovo ore district is centred on the exposed section of a Lower Oligocene volcano and consists of radially disposed Pb–Zn-precious metal veins and attendant intermediate sulfidation wallrock alteration. Earlier high sulfidation and potassic porphyry style alterations are found in the centre of the district spatially associated with monzonitic intrusions. The total duration of all mineralization and alteration was ca. 300 ka. Stable isotope analyses (S, O, H) have been carried out on a suite of sulfides, sulfates and silicates from the mineralization, high and intermediate sulfidation alterations and a suite of basement rocks. These data range between the following limits: \(\delta ^{{34}} S_{{sulfides}} = - 1.2\;\operatorname{to} \; + 6.8\,\,{\text{:}}\;\delta ^{{34}} S_{{sulfates}} = \; + 21.4\;{\text{to}}\; + 24.9\;\,\,;\;\delta ^{{18}} O_{{sulfates}} \; = \; + 5.8\;\operatorname{to} \; + 11.6\,\,;\;\delta D_{{sulfates}} = \; - 35.1\,\;\operatorname{to} \, - \;67.1\;\,:\;\delta ^{{18}} O_{{silicates}} \; = \; + 5.2\,\,{\text{to}}\; + \;13.5\;\,;\;\delta D_{{\operatorname{silicates} }} \; = \; - 36.3\;to\; - 77.0\;\). We also analysed δD of fluid inclusions in quartz and barite for which we obtained, respectively, the ranges of −43.6 to −78.6 and −58.4 to −67.1‰. The data show that high sulfidation alteration was dominated by magmatic fluids with minor meteoric water, whereas the fluids responsible for the intermediate sulfidation alteration were essentially magmatic. The fluids responsible for the intermediate sulfidation Pb–Zn mineralization were mixed magmatic–meteoric and certainly contained a significant meteoric component. Sulphur is likely derived from basement and/or igneous sources. The evolution of alteration and mineralization styles from potassic, porphyry copper style to high sulfidation to intermediate sulfidation can be understood in terms of changing ore fluid composition resulting from an increasing permeability of the system and an increasingly remote source of magmatic fluid with time. These changes link directly to the geological evolution of this volcanic centre.


Stable isotopes Pb–Zn mineralization Alteration Madjarovo Bulgaria 



We thank Terry Donnnelly and Alison MacDonald for the technical support during stable isotope analyses and Barry Fulton for the diagrams. SUERC is funded by Natural Environment Research Council (NERC) and the Scottish Universities Consortium. A.J.B. is funded by the NERC support of the Isotope Community Support Facility at SUERC. We thank Thomas Wagner of Tübingen University for the discussions and for allowing the use of his program for calculating O isotope trajectories resulting from boiling, cooling and mixing. We gratefully acknowledge the constructive reviews of Andrew Campbell and Jon Naden.


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© Springer-Verlag 2007

Authors and Affiliations

  • Clive M. Rice
    • 1
  • Richard J. McCoyd
    • 1
  • Adrian J. Boyce
    • 2
  • Peter Marchev
    • 3
  1. 1.Department of Geology and Petroleum GeologyUniversity of AberdeenAberdeenUK
  2. 2.Scottish Universities Research and Reactor CentreScotlandUK
  3. 3.Geological Institute, Bulgarian Academy of SciencesSofiaBulgaria

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